The synthesis of 6-trifluoroethyl-l-lysine: a method to introduce functionality at C-6 of l-lysine

Described is a method of introducing trifluoroalkyl groups at C-6 of lysine. This chemistry has the potential to introduce a variety of functionality at C-6 of lysine.     

Standardization of BSE rapid test performances and experiences gathered during the implementation of large-scale testing

The accumulation of pathological prion protein is used as a diagnostic marker for transmissible spongiform encephalopathies. According to European Union (EU) regulations cattle older than 30 months of age (Germany, France, Italy, and Spain by national law >24 months) and slaughtered for human consumption must be tested by using rapid tests for bovine spongiform encephalopathy (BSE). Likewise fallen stock and clinically affected animals must be tested. This article gives a short overview of the incidence of BSE in Europe. The diagnostic hierarchy, i.e., the officially approved methodology for the confirmation of suspect rapid test cases, and the organization of the numerous laboratories involved in this large-scale testing for BSE are described. Special emphasis is given to necessary quality control measures currently in place for BSE rapid testing laboratories and to measures intended to assure a consistent performance of the commercially available rapid test kits.Presented at BERM-9—Ninth International Symposium on Biological and Environmental Reference Materials, 15–19 June 2003, Berlin, Germany.     

Transport of surface-modified iron nanoparticle in porous media and application to arsenic(III) remediation

The surface-modified iron nanoparticles (S-INP) were synthesized, characterized and tested for the remediation of arsenite (As(III)), a well known toxic groundwater contaminant of concern. The S-INP material was fully dispersed in the aqueous phase with a particle size distribution of 2–10 nm estimated from high-resolution transmission electron microscopy (HR-TEM). X-ray photoelectron spectroscopy (XPS) revealed that an Fe(III) oxide surface film was present on S-INP in addition to the bulk zero-valent Fe⁰ oxidation state. Transport of S-INP through porous media packed in 10 cm length column showed particle breakthroughs of 22.1, 47.4 and 60 pore volumes in glass beads, unbaked sand, and baked sand, respectively. Un-modified INP was immobile and aggregated on porous media surfaces in the column inlet area. Results using S-INP pretreated 10 cm sand-packed columns containing ∼2 g of S-INP showed that 100 % of As(III) was removed from influent solutions (flow rate 1.8 mL min⁻¹) containing 0.2, 0.5 and 1.0 mg L⁻¹ As(III) for 9, 7 and 4 days providing 23.3, 20.7 and 10.4 L of arsenic free water, respectively. In addition, it was found that 100% of As(III) in 0.5 mg/L solution (flow rate 1.8 mL min⁻¹) was removed by S-INP pretreated 50 cm sand packed column containing 12 g of S-INP for more than 2.5 months providing 194.4 L of arsenic free water. Field emission scanning electron microscopy (FE-SEM) showed S-INP had transformed to elongated, rod-like shaped corrosion product particles after reaction with As(III) in the presence of sand. These results suggest that S-INP has great potential to be used as a mobile, injectable reactive material for in-situ sandy groundwater aquifer treatment of As(III).     

Structure and Magnetic Properties of Ce3Ge0.66In4.34 and Ce11Ge4.74In5.26

New indides Ce₃Ge_0.66In_4.34 and Ce₁₁Ge_4.74In_5.26 were synthesized from the elements by arc‐melting and subsequent annealing at 870 K. Single crystals were grown through special annealing procedures in sealed tantalum tubes in a high‐frequency furnace. Both compounds were investigated on the basis of X‐ray powder and single crystal data: I4/mcm, La₃GeIn₄ type, a = 848.8(1), c = 1192.0(2) pm, Z = 4, wR2 = 0.0453, 499 F² values, 17 variables for Ce₃Ge_0.66In_4.34 and I4/mmm, Sm₁₁Ge₄In₆ type (ordered version of the Ho₁₁Ge₁₀ type), a = 1199.3(2), c = 1662.0(3) pm, wR2 = 0.0507, 1217 F² values, 41 variables for Ce₁₁Ge_4.74In_5.26. The Ce₃Ge_0.66In_4.34 structure shows a mixed Ge/In occupancy on the 4c Wyckoff position. This site is octahedrally coordinated by cerium atoms. These octahedra share all edges, leading to a three‐dimensional network. The latter is penetrated by a two‐dimensional indium substructure which consists of flattened tetrahedra at In–In distances of 291 and 300 pm. The Ce₁₁Ge_4.74In_5.26 structure contains three crystallographically independent germanium sites. The latter are coordinated by eight or nine cerium neighbors. These CN8 and CN9 polyhedra are condensed to a complex network which is penetrated by a three‐dimensional indium network with In–In distances of 301–314 pm. The 16m site shows a mixed In/Ge occupancy. Chemical bonding in both compounds is dominated by the p elements. Both ternaries studied exhibit localized magnetism due to the presence of Ce³⁺ ions. The compound Ce₃GeIn₄ remains paramagnetic down to 1.72 K, whereas Ce₁₁Ge₄In₆ orders ferromagnetically at T_C = 7.5 K.     

The determination of manganese by electrothermal atomic absorption spectrometry with a graphite furnace at constant temperature

Many of the interferences reported earlier for the determination of manganese in a graphite furnace were not found when a modern graphite furnace was used. At high levels of chloride matrix, an interference which was observed in the modern furnace was reduced when manganese was determined under constant temperature conditions. In this work, the sample was introduced on a tungsten wire after the graphite furnace had reached a constant, preset temperature. Drying and ashing were accomplished outside the atomization furnace, reducing contamination from matrix materials.     

An NMR study of the rotational barriers in cobalt-stabilized carbocations: X-ray crystal structures of (η-C4Ph4)Co-(η-C5H4R), where R is CH3CO, CHO, CH(Bu)OH

Treatment of the aldehyde (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C₅H₄-CHR⁺ linkage on the NMR time-scale. These data indicate a minimum value for the barrier to rotation of 15 kcal mol⁻¹, but it is certainly much higher, indicating a considerable degree of C-C double bond character. X-ray crystal structures of 4b, 5 and also of the ketone (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-C(O)CH₃ (4a) are reported. The secondary alcohol 5 exhibits disorder in the solid state because of the presence of diastereomers as a consequence of the stereogenic center at the α-carbon and the clockwise or anticlockwise propeller orientations of the tetraphenylcyclobutadiene ligand.     

Is a small number of charge neutralizations sufficient to bend nucleosome core DNA onto its superhelical ramp?

X-ray diffraction structures of the nucleosome core particle along with a variety of experiments are consistent with the idea that an important source of the free energy holding DNA to the superhelical ramp on the histone octamer surface is obtained from a relatively small amount of electrostatic neutralization of the DNA phosphate charge by positively charged histone groups, especially arginine residues. Here we present a theoretical analysis of a simple model that emphasizes the competition between the high degree of bending of the stiff DNA molecule required for its tight curvature on the histone octamer and the neutralization of the DNA phosphate charge by basic histone residues. Our calculation accounts for the strong influence of condensed counterions on the electrostatic interactions. We find that the minimum amount of free energy required to bend DNA into axial conformity with the superhelical ramp at physiological salt concentration can be provided by a scant 6% neutralization of the phosphate charge, in close correspondence to the stoichiometric neutralization of phosphate charge by the arginine side chain that intrudes into the inward-facing minor groove of each DNA double helical turn.